CN101855175B - Removal of residual sulfur compounds from a caustic stream - Google Patents

Removal of residual sulfur compounds from a caustic stream Download PDF

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CN101855175B
CN101855175B CN2008801154616A CN200880115461A CN101855175B CN 101855175 B CN101855175 B CN 101855175B CN 2008801154616 A CN2008801154616 A CN 2008801154616A CN 200880115461 A CN200880115461 A CN 200880115461A CN 101855175 B CN101855175 B CN 101855175B
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caustic alkali
sulphur
ppm
weight
clean unit
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CN101855175A (en
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张铁军
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Merichem Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/08—Recovery of used refining agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3265—Non-macromolecular compounds with an organic functional group containing a metal, e.g. a metal affinity ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Abstract

A process for the removal of residual sulfur compounds from a liquid caustic stream is disclosed. One embodiment of my invention adsorbs disulfides from a caustic stream using an activated carbon adsorbent while another combines both oxidation and adsorption in single step to remove residual sulfur compounds from a rich caustic stream using metal phthalocyanine supported on a solid adsorbent. This process is especially useful as a polishing step in a caustic regeneration process flow scheme.

Description

Remove the residual sulphur compound from caustic alkali stream
Technical field
The method that relate generally to of the present invention is removed the residual sulphur compound from caustic liquid alkali stream (caustic stream).More specifically, one embodiment of the present invention use acticarbon from caustic alkali stream absorption disulphide.In another embodiment, the metal phthalocyanine of working load of the present invention on solid adsorbent will adsorb and catalyzed oxidation combines, to remove the residual sulphur compound from caustic alkali stream.Also the present invention can be incorporated into and adopt caustic regeneration from hydrocarbon, to remove in the technology of amounts of sulphur contaminants as purifying method (polishing process), thereby the needs that the solvent wash of costliness is handled are minimized.
Background technology
It is known using caustic alkali to remove amounts of sulphur contaminants (especially mercaptan) from hydrocarbon stream.Equally, by enrichment caustic alkali stream (rich caustic stream) being contacted with solid catalyst and these mercaptan oxidations being become disulphide, it also is known separating disulphide from the caustic alkali of handling then.No matter what use is oxidation and/or separating treatment, always there is the residual sulphur compound to remain in the caustic solution of handling.Pressing for more economically, also under the situation of compacter method, needing with more small-sized, more efficient purifying method replaces traditional solvent wash, to obtain the not caustic alkali of the hydrocarbon of the be reused for processing sulphur pollution of sulfur-bearing.
The rules of the US Clean Air Act of nineteen ninety have reached its summit in the North America, the summation (gasoline pool) that requires to concoct the various components of usefulness for gasoline product contains the sulphur that is less than 10-wppm.Viewpoint from reality, this means, the pipeline of considering residual wall from the previous transportation sulphur that " adheres to (clingage) " pollutes and the precision of Clean Air Act specified test, and the refinery summation of concocting the various components of usefulness for gasoline product of preparation usually contains the sulphur that is less than 5-wppm.
Another result of the Clean Air Act of nineteen ninety was the small-sized inefficient refinery of having closed the U.S., was reduced to the 175 tame refinerys that are less than in 2007 from more than 330 tame refinerys in 1980.Do not build new refinery in the past 25 years, but the gasoline demand of the U.S. has been satisfied in the expansion production of refinery and import.
Already present refinery has also reached the requirement of stricter fluid catalytic cracking unit operation (higherseverity Fluid Catalytic Cracking Unit operations) to reduce the roasting kiln fuel quantity, simultaneously the gasoline of the outer higher octane of delivery capacity and increase olefin yield.These alkene are propane/propylene and butane/Trimethylmethane/iso-butylene.These are raw materials of following procedure of processing (it is alkylation).Some refinerys are according to their economic model alkylation amylene.
Most refinerys use HF (hydrofluoric acid) or sulfuric acid alkylation unit to come propylene and the butylene of alkylation mixed butene or mixing.Alkylation is that Trimethylmethane and olefine reaction are with the process of the paraffinic hydrocarbons of preparation branching.Because sulphur is harmful to alkylation process, so most refinery uses the caustic alkali treatment system to be present in the methyl mercaptan that is easy to extract in mixed olefins liquefied petroleum gas (" the LPG ") stream and the propyl group mercaptan of ethanethio and difficult extraction with extraction in position.
Usually, handle for caustic alkali, use liquid-liquid-liquid contactor, in some cases, use fiber-membrane contactor, as United States Patent (USP) 3,758,404; 3,977,829 and 3,992, described in 156, incorporate all these patents mode by reference into this paper.In order to save caustic alkali, almost always be to use the caustic regeneration agent.Typical process flow for the treatment of LPG comprises: at first use at least a liquid-liquid-liquid contactor to carry out caustic alkali and handle to extract amounts of sulphur contaminants (being generally mercaptan) from the LPG feed, thereby produce caustic solution or so-called enrichment caustic alkali that " (spent) of inefficacy " is rich in mercaptan; Separate the LPG in the contactor; Oxidation enrichment caustic alkali to be changing into mercaptan disulphide (being commonly referred to disulfide oil (" DSO ")), thereby generates " oxidation " caustic solution; Use gravity separator to separate DSO from the caustic solution of oxidation then.In some cases, with the particle coal bed with as the gravity settling equipment coupling of coalescer, separate from the caustic alkali of oxidation with further promotion DSO.In case DSO is removed, the caustic alkali of regeneration further can be handled, and then circulation, wherein it is mixed to be incorporated in liquid-liquid-liquid contactor with the fresh caustic of replenishing and use, to handle the LPG feed.More typically, need further purifying method, so that unconverted mercaptan and residual DSO are reduced, preferably be lower than 5 ppm by weight (in sulphur).It is undesirable having a large amount of mercaptan in the caustic alkali of regeneration, because can cause the loss of extraction efficiency and cause the possibility that forms disulphide in the downstream.Regeneration caustic alkali in exist a large amount of DSO cause undesirable during hydrocarbon-caustic alkali extraction process DSO return to or strip to hydrocarbon.
Solvent wash is known technology, through being commonly used for purifying step to extract residual DSO from caustic alkali.Yet because mass transfer and equilibrium-limited, these solvent wash unit operations need a plurality of stages usually, and fund and running cost are higher.In addition, solvent wash is invalid for removing mercaptan from caustic alkali.Similarly, centrifuging and membrane sepn have expensive and can not reach the problem of the sulphur that is lower than 5 ppm by weight.
Adsorption cleaning (adsorptive polishing) is operable another kind of technology.Adsorption desulfurize has been applied to from hydrocarbon such as gasoline and diesel oil, remove sulphur compound.Example is shown in United States Patent (USP) 7,093,433; 7,148,389; 7,063,732; With 5,935,422.Yet the sorbent material of reporting in these patents and other document is invalid in the caustic alkali medium.
Therefore, still need to develop a kind of technology, this technology can be removed disulphide and mercaptan from caustic alkali economically as purifying method, to realize being lower than the sulphur of 20 ppm by weight, preferably is lower than 5ppm and most preferably is lower than 2ppm.
Present method uses oxidation and the fractionation by adsorption (OAS) of single step to remove disulphide and mercaptan from caustic solution.Described OAS method replaces solvent wash as purifying step, and, when when most of DSO after separating uses, residual mercaptan is changed into DSO and remove whole residual DSO (comprising the DSO that forms from the mercaptan original position).And because fund and running cost are minimized, present method is compared very economical with the traditional method that is used for removing from caustic solution the residual sulphur compound.More detailed description below according to the present invention, these and other advantage will become apparent.
Summary of the invention
As mentioned above, the present invention relates to remove the method for residual sulphur compound remaining in the caustic solution in oxidation that forms during the caustic regeneration.On the one hand, the present invention can be adsorbed on residual DSO on the acticarbon, makes the caustic alkali stream that reclaims contain and is lower than 20ppm weight, is preferably the sulphur compound that is lower than 5ppm weight (in sulphur).
Although it is known using oxidation as means mercaptan to be changed into DSO, this currently known methods does not change into DSO with all mercaptan usually, therefore stays nearly 5% or more mercaptan in oxidation reaction product stream.Before the present invention, described unconverted mercaptan is keeping not transforming in the caustic alkali of regeneration always, and this influences caustic alkali-hydrocarbon extraction process subsequently unfriendly.Before the present invention, never will be appreciated that, these residual mercaptan can be changed into DSO and adsorb with the residual DSO that in sepn process (this process is carried out after the oxidation at enrichment caustic alkali stream usually), does not remove, all in single step, carry out.Present method can be readily integrated in new and the already present caustic regeneration technical process, wherein when when contacting, producing enrichment caustic alkali stream from the amounts of sulphur contaminants of LPG and other hydrocarbon stream and barren caustic alkali (leancaustic).
Disulfide oil used in this application or DSO are intended to comprise the possible disulphide mixture of (comprising dimethyl disulphide, diethyl disulphide, methylethyl disulphide and senior disulphide).Similarly, term mercaptan is intended to comprise and is similar to pure and mild phenol, but contains any compound in the class organosulfur compound of the sulphur atom that replaces Sauerstoffatom, and especially comprises mercaptide.Contain-SH is " mercaptan " as the compound name of the main group that directly connects carbon.
One aspect of the present invention relates to the method for removing the residual sulphur compound from the caustic alkali feed streams, described method comprises the combination following steps: the caustic alkali feed streams that will contain caustic alkali and sulphur compound is incorporated in the clean unit (polishing unit), wherein said sulphur compound is lower than 500 ppm by weight in sulphur, preferably be lower than 100 ppm by weight, and most preferably be lower than 50 ppm by weight; Described caustic alkali stream is contacted with solid adsorbent beds; Be incorporated into disulphide in the clean unit in the absorption of described sorbent material as the part of the sulphur compound in the caustic alkali feed streams; And remove the caustic alkali apoblema of purification from clean unit, the caustic alkali apoblema of described purification comprises and is lower than 20 ppm by weight, preferably is lower than 5 ppm by weight, and most preferably is lower than the sulphur compound of 2 ppm by weight (in sulphur).Preferred sorbent material is the gac with high DSO adsorptive power, and it has 0.5-1.5cc/g BJH N 2Void volume and/or 500-2,000m 2The surface-area of/g BET is by the raw material manufacturing such as coal, brown coal, timber, peat, Nux Canarii albi (olivepit) and coconut husk.Example is Norit based on MRX, the MeadWestvaco of brown coal based on the Nuchar series of timber, the Calgon CPG gac based on coal.Gac can be particle or the pellet of extruding (extruded pellets).Service temperature of the present invention is about 50 to about 212 °F, is preferably about 75 to about 175 °F, and most preferably is about 75 to about 150 °F.Present method can be implemented at environmental stress or the working pressure that runs into usually in the caustic regeneration technical process.
Another aspect of the present invention relates to the method for removing the residual sulphur compound from the caustic alkali feed streams, described method comprises the combination following steps: the caustic alkali feed streams that will contain caustic alkali and sulphur compound is incorporated in the clean unit, wherein said sulphur compound is lower than 500 ppm by weight in sulphur, preferably be lower than 100 ppm by weight, and most preferably be lower than 50 ppm by weight; Oxygenant is incorporated in the clean unit; In the presence of the catalyst bed that contains supported metal phthalocyanine, make the mixing of caustic alkali stream and oxygenant and contact; The mercaptan that will exist as the part of described sulphur compound changes into disulphide; The disulphide that is formed by the mercaptan original position in the absorption of described support of the catalyst and be incorporated into disulphide in the clean unit as the part of the sulphur compound in the caustic alkali feed streams; And remove the caustic alkali apoblema of purification from clean unit, the caustic alkali apoblema of described purification comprises and is lower than 20 ppm by weight, preferably is lower than 5 ppm by weight, and most preferably is lower than the sulphur compound of 2 ppm by weight (in sulphur).
According to following contained detailed description of the preferred embodiment, it is clearer that the purpose of these and other will become.
Description of drawings
The synoptic diagram of a kind of possible embodiment of Fig. 1 the inventive method, this embodiment uses absorption separately or uses the combination of oxidation and absorption in single step, to remove the residual sulphur compound from caustic alkali stream, described caustic alkali stream has lived through oxidation to be separated with the most of the DSO that generates in the oxidation of enrichment caustic alkali.
Fig. 2 is the synoptic diagram of efficient of the present invention, and the caustic alkali feed that wherein will contain average 86 ppm by weight sulphur compounds purifies to containing the mercaptan that is lower than 1 ppm by weight and be lower than 2 ppm by weight DSO in the caustic alkali product.
Embodiment
As mentioned above, the present invention relates to for the new method that is incorporated into the caustic regeneration technical process, design this method and remove the residual sulphur compound for most of after separating of the DSO that between oxidation period, forms from the caustic alkali stream of oxidation.A kind of concrete application of the present invention relates to the purifying method of removing the residual sulphur pollutent from the caustic alkali stream of oxidation, and described residual sulphur pollutent is harmful in the caustic alkali of hydrocarbon such as LPG is handled particularly to downstream process.More specifically, the present invention has eliminated and has used expensive solvent wash to obtain the needs of barren caustic alkali, and described barren caustic alkali has the sulphur compound that is lower than 5ppm by weight and is suitable for the hydrocarbon of recirculation contact stain.
Fig. 1 shows one embodiment of the present invention, wherein will be supplied to caustic alkali treating part 3 by circuit 1 by the LPG feed of mercaptan compound such as methyl mercaptan thing and the pollution of ethanethio thing.The specific design of caustic alkali treating part is not crucial for the present invention; Yet preferred design comprises the staged contactor with the convection current constructor, and most preferred contactor structure uses tunica fibrosa liquid-liquid-liquid contactor.These and other contactor structure is well known to a person skilled in the art.Barren caustic alkali is supplied to contactor treating part 3 by circuit 5, and it contacts with the LPG that introduces by circuit 1 at this place.The caustic alkali of Shi Yonging can be the known any kind in hydrocarbon desulfurization field in the present invention, comprises the solution that contains NaOH, KOH, Ca (OH) 2, Na2CO3, ammonia, organic acid extract (extraction oforganic acids) or their mixture.Preferably, described caustic alkali comprises potassium hydroxide aqueous solution and aqueous sodium hydroxide solution, and concentration is about 1% to about 50%, and more preferably about 3% to about 25%, is more preferably about 5% to about 20%, in the weight of alkali metal hydroxide.
The LPG that is substantially free of sulphur is removed and is used for subsequently technology from contactor part 3 by circuit 7, for example, in alkylation.Be substantially free of total sulphur content＜150ppm that sulphur refers to LPG, be preferably＜20ppm and more preferably＜10ppm.Caustic solution from contactor part 3 is the enrichment caustic solution of removing by circuit 9.Enrichment caustic alkali contains from the mercaptan that is mercaptide and other amounts of sulphur contaminants form of LPG feed extraction.
To be supplied to oxidizer 10 from the enrichment caustic alkali of caustic alkali treating part then.The same with liquid-liquid-liquid contactor, the specific design of oxidizer is not crucial for the present invention, can use many oxidizer design, for example bubble oxidizer, on-catalytic solid packing and solid catalysis technology.Preferred oxidizer is such oxidizer, that is, described oxidizer contains the Solid Bed of the catalyzer (being preferably the catalyzer that contains reactive metal such as cobalt) that is immersed on solid carrier such as the gac.Most preferred catalyzer is that Merichem Company is with trade name ARI TMThe catalyzer that-120L sells.In a kind of selectable embodiment of the present invention, small volume solvent streams 11 is introduced oxidizer 10 with enrichment caustic alkali stream.This solvent streams can be mixed with enrichment caustic alkali before entering oxidizer, perhaps injected oxidizer as independent fluid.Described solvent can be any light hydrocarbon that helps the DSO after oxidation in downstream to separate with caustic solution.Can use the mixture of the hydrocarbon of any relative lightweight or this hydrocarbon as solvent in the present invention, yet preferred solvent comprise petroleum naphtha and kerosene.How to improve the accurate mechanism of separating of DSO and oxidation caustic alkali although know described solvent also imprecisely, a kind of theory is, described solvent has the DSO solubleness more much higher than caustic alkali, and their poor solubility provides the extraction motivating force.By in the tunica fibrosa equipment of higher interfacial surface area is provided, implementing this process, further amplified this effect.Not crucial especially for the present invention with enrichment caustic alkali or the amount (based on the percent by volume of enrichment caustic alkali feed) that is injected into the solvent in the oxidizer individually, as long as use minimum, get final product to improve the downstream separation performance.As mentioned above, only need the solvent of small volume, the preferable range of minimum solvent injection rate is extremely about 10.0vol% of about 0.1vol%, is preferably about 0.5vol.% to about 5.0vol.%, based on the enrichment caustic alkali feed by circuit 9 supplies.
Except with enrichment caustic alkali and solvent supply to oxidizer, oxygenant such as air, hydrogen peroxide or other oxygen-containing gas are introduced oxidizers by circuit 12.The amount that is added into the oxygenant of oxidizer is enough to realize that the mercaptan compound that initially is present among the LPG with more than 95% is oxidized to disulphide, most preferably reaches the oxidation more than 99%.The preferable range that is used for the operational condition of oxidizer comprise about 75 °F to about 200 temperature with up to the caustic alkali flow velocity of 10LHSV, but be preferably about 100 °F to about 150 °F and be lower than 5LHSV.The working pressure of present method is not crucial, handles stream maintenance liquid state as long as make.
With the effluent in the oxidizer 10, or the caustic alkali of oxidation (it is the mixture of caustic alkali, DSO and residual mercaptan (for the form of mercaptide)) removes and is passed to separator 14 by circuit 13 from oxidizer 10, uses any known separation techniques (being generally gravitational settler) that most of DSO is separated with caustic alkali at this place.
In the operating period of separator 14, form two layers in the bottom of collection container 21; The lower floor 23 and the upper strata 22 that is contained in the most of DSO that forms during the oxidation step that contain caustic solution.As mentioned above, Fig. 1 also shows selectable embodiment, wherein adds little solvent streams in the upstream of oxidizer 10.When using this possibility, the DSO of solvent in upper strata 22 that adds removed.Waste gas (if present) is removed by circuit 15 from collection container 21 tops.DSO in the upper strata 22 is removed and delivers to storage or be used for further processing by circuit 16 from separation vessel 14.
Be chosen in the residence time in the separator 14, to remove DSO mutually substantially from caustic alkali, all the aimed concn of sulphur compound (comprising mercaptan) more particularly is lower than 100ppm for being lower than 500ppm by weight.The typical residence time of gravitational settler is 90 minutes or longer.
Regulate by the speed of circuit 17 except the caustic solution in the sub-cloud 23, reach 500ppm or the lower necessary suitable residence time to keep the amounts of sulphur contaminants content that makes in this layer.To flow the caustic solution guiding clean unit 24 of the separation in 17 then, at this place residual DSO will be adsorbed onto on the solid adsorbent (being preferably gac).Contain in the situation of mercaptan at caustic alkali, gac contains metal catalyst so that mercaptan is changed into disulphide.Then these disulphide are adsorbed onto on the solid catalyst.For helping this conversion of mercaptan, also oxygenant is incorporated into clean unit 24 (with dashed lines 20 illustrates).The amount that is incorporated into the oxygenant in the clean unit should be that mercaptan oxidation is become at least one times of the needed stoichiometric amount of disulphide, is preferably twice.As mentioned above, preferred solid adsorbent is that volume of voids is 0.5-1.5cc/g BJH N 2And/or surface-area is 500-2,000m 2The gac of/g BET.Described metal catalyst is preferably metal phthalocyanine, most preferably, and wherein said metal chosen from Fe and cobalt, or the mixture of these metals, and load on the solid adsorbent.Randomly, the present invention can comprise manipulation of regeneration, periodically described solid adsorbent is carried out manipulation of regeneration thus.Those skilled in the art will appreciate that the renovation process that there is a large amount of reproducing adsorbent beds (original position and from (off-column) of post), comprise ion-exchange, solvent backwash, calcining, pyrolysis etc.Employed concrete grammar depends on selected sorbent material, whether has economy and the validity of catalyzer and gross decontamination process.
The present invention can prepare the barren caustic alkali that amounts of sulphur contaminants is lower than 5 ppm by weight.Then the caustic alkali of final purifying is removed from container 24 as barren caustic alkali, and be recycled to caustic alkali treating part 3 by circuit 5.
Embodiment
For illustrating wonderful and unexpected effect of the present invention, the chamber of experimentizing test.Fill 1-inch diameter and 4 feet high posts with gac, the preimpregnation of described gac has the cobalt phthalocyanine.The feed caustic alkali that will contain average 86 ppm by weight sulphur compounds is incorporated in the post with airflow, and described airflow provides with the amount more than five times that mercaptan is completely oxidized to the needed stoichiometric amount of disulphide.This post is maintained about 125 and 25psig.
Effect of the present invention is shown in Fig. 2.When feed caustic alkali contained average 86 ppm by weight sulphur compounds, described product caustic alkali contained and is lower than 1 ppm by weight mercaptan and is lower than 2ppm disulphide.Total sulphur compound is starkly lower than 5 ppm by weight.
Also surprisingly, this effect is consistent not considerable change (breakthrough) after going through at least 137 hours operate continuously.During this period, the active-carbon bed sulphur compound that has adsorbed about 17 weight % (in sulphur) of itself weight.
Final when saturated when described carbon bed, it can be used for a plurality of life cycles with new material bed replacement or regeneration.Economy and the validity of regeneration have determined this selection.
The description of previous embodiment has disclosed general aspects of the present invention fully, make other people have the various application that knowledge can easily change and/or adapt to this embodiment now by using, and do not depart from purport, therefore this changes and adaptation expectation are included in the meaning and scope of equivalent of disclosed embodiment.Will be appreciated that the application's wording or term are used for illustration purpose, unrestricted effect.
The means, material and the step that are used for the function of the various disclosures of enforcement can take plurality of optional to select form, and do not depart from the present invention.Therefore, the expression that is used in combination with functional statement that can in specification sheets and claim, find " ... method (means to...) " and " be used for ... method (meansfor...) " or any method steps wording, a kind of embodiment or the numerous embodiments that in specification sheets, disclose above no matter whether accurately being equal to, all be intended to limit and cover structure arbitrarily, physics, chemistry or electricity element or the structure that can exist now or exist in the future, or arbitrary method step, that is, can use other method or the step that realizes identical function; And within the scope of the appended claims, give these and express the wideest explanation.

Claims (15)

1. remove the method for residual sulphur compound from the caustic alkali feed streams, described method comprises the combination following steps:
A) pre-oxidation that will contain caustic alkali and sulphur compound is incorporated in the clean unit with the caustic alkali feed streams that separates, and wherein said sulphur compound is lower than 500 ppm by weight in sulphur;
B makes described caustic alkali feed streams contact with solid adsorbent beds in described clean unit;
C) adsorb disulphide at described adsorbent bed, this sulfurous gas is that the part as the sulphur compound in the described caustic alkali feed streams is incorporated in the described clean unit; With
D) remove the caustic alkali apoblema of purification from described clean unit, the caustic alkali apoblema of this purification comprises the sulphur compound that is lower than 20 ppm by weight (in sulphur).
2. the method for claim 1, wherein said sulphur compound is lower than 100 ppm by weight in sulphur in described caustic alkali feed streams.
3. the method for claim 1, wherein said sulphur compound is lower than 5 ppm by weight in sulphur in the caustic alkali apoblema of described purification.
4. the method for claim 1, wherein said sorbent material is gac.
5. the method for claim 1 is wherein carried out manipulation of regeneration at least a portion in the described sorbent material.
6. handle the method for the caustic alkali stream of enrichment mercaptan, described method comprises the combination following steps:
A) the enrichment caustic alkali stream that will contain mercaptan compound is supplied to oxidizer;
B) in the presence of oxygenant with described mercaptan compound with 90% or higher level of conversion be oxidized to disulfide oil (DSO), and form the mixture contain DSO and caustic alkali and residual mercaptan;
C) mixture that forms in the described step b) is shifted out and described mixture is introduced separating device from described oxidizer;
D) by making described mixture in collecting region, form two different liquid levels, the lower floor that contains the caustic alkali phase with contain DSO upper strata mutually, the major part among the described DSO is separated in described separating device with described caustic alkali;
E) by taking out described upper strata described DSO is removed from described separating device, and by taking out described lower floor the described caustic alkali that is lower than 500 ppm by weight sulphur compounds that contains is removed from described separating device;
F) described caustic alkali stream from step e) is incorporated into as feed streams contains in the active-carbon bed clean unit, described gac has 0.5-1.5cc/g BJH N 2Volume of voids and/or 500-2,000m 2The surface-area of/g BET;
G) be incorporated into disulphide in the described clean unit in gac absorption as the part of the sulphur compound in the caustic alkali stream of described step f); With
H) remove the caustic alkali apoblema of purification from described clean unit, the caustic alkali apoblema of described purification comprises the sulphur compound that is lower than 20 ppm by weight (in sulphur).
7. method as claimed in claim 6, wherein said sulphur compound is lower than 100 ppm by weight in sulphur in the caustic alkali feed streams of described clean unit.
8. method as claimed in claim 6, wherein said sulphur compound is lower than 5 ppm by weight in sulphur in the caustic alkali apoblema of described purification.
9. method as claimed in claim 6, the caustic alkali stream that wherein is incorporated into described clean unit comprises the mercaptan less than 50 ppm by weight.
10. method as claimed in claim 6 is wherein carried out manipulation of regeneration at least a portion gac.
11. accounting in sulphur, method as claimed in claim 6, wherein said sulphur compound be lower than 5 ppm by weight in the caustic alkali apoblema of described purification.
12. method as claimed in claim 6, wherein
I is incorporated into oxygenant in the described clean unit;
Ii in the presence of the catalyst bed that contains supported metal phthalocyanine, makes described caustic alkali stream and oxygenant mixing and contacts in described clean unit;
Iii changes into disulphide by the mercaptan that oxidising process will exist as the part of the sulphur compound in the caustic alkali stream of described step f); With
The disulphide that iv forms in the oxidising process of the described step I ii of described support of the catalyst absorption and be incorporated into disulphide in the described clean unit as the part of the sulphur compound in the caustic alkali stream of described step f).
13. method as claimed in claim 12, wherein said oxygenant are air or at least a oxygen-containing gas.
14. method as claimed in claim 12, wherein said metal are selected from cobalt, iron and their mixture.
15. method as claimed in claim 12 wherein is incorporated into solvent in the oxidizer in step a) and removes the described solvent with DSO in step e).
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